JP2010120780A - Double pore organic chain inorganic porous body, method for producing double pore organic chain inorganic porous body, and method for producing column for chromatography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a double pore organic chain inorganic porous body which has excellent alkali resistance, and further exhibits excellent separability when being used as a filler in chromatography, and to provide a method for producing the same. <P>SOLUTION: The method comprises: a gelling stage where an organic chain alkoxy silane is charged inside an acid solution comprising an alkali generating compound decomposed by heating and generating an alkali component and an organic polymer having a phase separation induction action so as to hydrolyze the organic chain alkoxy silane, and thereafter, heating is performed, and, while decomposing the alkali generating compound, the organic chain alkoxy silane is polycondensed so as to form gel having a skeleton with a three-dimensional network structure; and a micropore forming stage where the obtained gel is subjected to hydrothermal treatment under alkali conditions so as to form micropores in the skeleton. The double pore organic chain inorganic porous body having a skeleton with a three-dimensional network structure composed of a silane polycondensate having an SiC bonded part in the molecules, and provided with micropores in the skeleton is obtained by the method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a membrane emulsification for producing a separation medium for chromatography, a porous body for blood separation, a sample concentration medium for environmental analysis, a porous body for a hygroscopic agent, a porous body for low molecular weight adsorption such as deodorant, and fine particles of uniform diameter Suitable for porous membranes used in the method, or porous bodies for enzyme supports and catalyst supports, a method for producing double porous organic chain inorganic porous bodies, and for chromatography The present invention relates to a method for producing a column.

In a liquid chromatography apparatus, generally, inorganic porous particles such as silica gel are packed in a column as a separation medium.
In this type of liquid chromatography system, the most effective way to improve the resolution is to reduce the size of the particles packed in the column, but it is necessary to reduce the size of the particles and at the same time obtain an appropriate flow rate for analysis. Pressure increases and the column length must be shortened.

Therefore, porous particles having a large surface area are used in order to obtain an appropriate sample load, but these exhibit low mechanical strength, which makes it difficult to perform uniform filling operations. Therefore, there is a limit to the particle size reduction for increasing the resolution in liquid chromatography. As long as the particle packed column is used under pressure feeding, it is not possible to escape from this restriction. Therefore, in order to obtain a high theoretical plate number in a short time, it is necessary to devise a technique for avoiding the high pressure accompanying fine particles.
In order to achieve high-performance separation in a short time, that is, at a high speed, a separation medium having a large flow path through which a solvent can flow at a low pressure and a small skeleton corresponding to the particle diameter of the filler is required.

  Therefore, in order to satisfy the above conditions, tetraethoxysilane is added to an acidic solution in which a water-soluble polymer such as polyethylene oxide and urea that decomposes by heating to generate an alkali component are uniformly dissolved. After injection, tetraethoxysilane was hydrolyzed and polycondensed below the decomposition temperature of urea to form a wet gel separated into a solvent-rich phase and a skeletal phase, that is, phase separation based on spinodal decomposition and sol-gel transition Are formed simultaneously to form a skeleton with macropores, and this wet gel is heated more than the thermal decomposition of urea to generate ammonia, and a part of the skeleton is dissolved in the skeleton by the generated ammonia. A method for producing an inorganic porous material in which fine pores are formed in a thin film has been proposed (see Patent Document 1).

  That is, in this method for producing an inorganic porous material, first, tetraethoxysilane is hydrolyzed and polycondensed in an acidic solution as in the conventional method for producing an inorganic porous material. Since the water-soluble polymer is uniformly dissolved therein, the wet phase is first composed of an island-like solvent-rich phase formed by phase separation from the aqueous phase portion and a skeleton phase composed of a silane polycondensate. A gel is formed.

Then, by heating this wet gel more than the thermal decomposition of urea, ammonia is generated, and the generated ammonia dissolves a part of the silane polycondensate that forms the skeleton phase to form micropores in the skeleton. Is done.
Therefore, when a water-soluble polymer is removed by heating and drying at the end, a skeleton part having a three-dimensional network structure that forms continuous pores having an average diameter of 100 nanometers or more is provided. A double-porous body having a pore shape or a bulk or monolith shape can be obtained.

  However, the double pore porous material obtained by the above production method has a problem with conventional alkali resistance.

Therefore, the inventors of the present invention, in the above method for producing a double pore porous body, instead of tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 1, It was thought that alkali resistance could be improved by using an organic chain alkoxysilane such as 2-bistrimethoxysilylethane and using a silane polycondensate having a SiC bond in the molecule as the skeleton.
However, when an organic chain alkoxysilane is polycondensed under the same conditions as in the above method to obtain a wet gel, the organic chain site is exposed on the external surface of the skeleton when used as a starting composition. Therefore, even after heating to decompose urea to make it alkaline, the organic chain portion hindered and fine pores could not be successfully formed in the skeleton.

JP 11-292528 A

  In view of the above circumstances, the present invention provides a double-pore organic chain inorganic porous body that exhibits excellent alkali resistance and exhibits excellent separation performance when used as a chromatography filler, and a method for producing the same. The purpose is to do.

  In order to achieve the above object, the double pore organic chain inorganic porous material according to the present invention has a three-dimensional network structure skeleton composed of a silane polycondensate having a SiC bond portion in the molecule. It is characterized by having fine holes inside.

  The method for producing a double-pore organic chain inorganic porous material according to the present invention includes an alkali-generating compound that decomposes by heating to generate an alkali component and an organic polymer that has a phase separation-inducing action. The organic chain alkoxysilane is introduced into the organic chain to hydrolyze the organic chain alkoxysilane, and then heated to decompose the alkali-generating compound while polycondensating the organic chain alkoxysilane to form a three-dimensional network structure skeleton. A gelation step for forming a gel having a micropore, and a micropore formation step for forming a micropore in the skeleton by hydrothermally treating the obtained gel under alkaline conditions.

In the present invention, the acid used in the acidic solution is not particularly limited, and examples thereof include acetic acid, nitric acid, hydrochloric acid, formic acid and the like, and among them, a weak acid such as acetic acid is preferable.
The pH of the acidic solution is not particularly limited, but the pH before polycondensation is preferably adjusted to 1 or more and less than 5. That is, if the acidity is too strong, it becomes difficult to form micropores in the skeleton portion, and if it is too weak, gelation is slow, which may cause a problem in productivity.

  In the present invention, the organic chain alkoxysilane means a compound in which 1 to 3 alkoxy groups are bonded to Si atoms and 3 to 1 organic groups are bonded so as to form a SiC bond. Examples include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 1,2-bistrimethoxysilylethane, and the like. These can be used alone or in combination.

The alkali-generating compound is not particularly limited, and examples thereof include organic compounds such as urea, hexamethylenetetramine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and the like. Amides are mentioned, and these can be used alone or in combination, and urea is particularly preferable.
The alkali-generating compound is not only added in advance to the acidic solution, but may be further added during gelation as necessary.

  The heating temperature during polycondensation is not particularly limited, but is preferably as low as possible if a predetermined amount of alkali component is generated. That is, if the heating temperature is too high, the solution boils, voids are generated, and a good skeleton may not be formed. Incidentally, when urea is used, since the decomposition temperature of urea is about 50 ° C. or higher, the heating temperature is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° C. or lower.

The organic polymer is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polyoxyethylene nonylphenyl ether, and ethylene oxide-propylene oxide copolymer. These may be used alone or in combination. It does not matter.
The blending ratio of the organic polymer can be appropriately adjusted according to the pore size of the skeleton part to be obtained.

Moreover, in the manufacturing method of the double pore organic chain inorganic porous material of this invention, you may make it add the solvent which micelleizes an organic polymer in an acidic solution.
The solvent for micelleizing the organic polymer is not particularly limited, and examples thereof include trimethylbenzene, methanol, butanol and the like, and these may be used alone or in combination.

Furthermore, the method for producing a chromatography column according to the present invention includes a method for producing a double-pore organic chain inorganic porous material of the present invention in a capillary, and a method for producing a double-pore organic chain inorganic porous material in a capillary. It is characterized by forming the body filled.
The material of the capillary is not particularly limited, and examples thereof include fused silica and polyether ether ketone (PEEK resin).

  As described above, the double pore organic chain inorganic porous material according to the present invention has a three-dimensional network structure skeleton composed of a silane polycondensate having a SiC bond portion in the molecule, and the fine structure is contained in the skeleton. Since the holes are provided, the alkali resistance is excellent. Therefore, chromatographic separation media used in the alkaline region, blood separation porous materials, environmental analysis sample concentration media, hygroscopic porous materials, deodorant and other low molecular weight adsorption porous materials, and uniform-sized fine particles are produced. It is suitable as a porous membrane used in the membrane emulsification method, or as a porous material for an enzyme carrier and a catalyst carrier.

  The method for producing a double-pore organic chain inorganic porous material according to the present invention includes an alkali-generating compound that decomposes by heating to generate an alkali component and an organic polymer that has a phase separation-inducing action. The organic chain alkoxysilane is introduced into the organic chain to hydrolyze the organic chain alkoxysilane, and then heated to decompose the alkali-generating compound while polycondensating the organic chain alkoxysilane to form a three-dimensional network structure skeleton. It is difficult to obtain so far because it comprises a gelation step for forming a gel having a gel and a micropore formation step for forming a micropore in the skeleton by hydrothermally treating the obtained gel under alkaline conditions. Thus, the double pore organic chain inorganic porous material of the present invention having excellent alkali resistance can be obtained.

That is, when an organic chain alkoxysilane is added to an acidic solution, the organic chain alkoxysilane is first hydrolyzed. Then, by heating to the decomposition temperature of the alkali generating compound, polycondensation while making the solution close to neutral, the skeleton of a three-dimensional network structure consisting of a silane polycondensate with many hydroxyl groups vulnerable to alkali on the surface A wet gel with parts is obtained.
The wet gel was further hydrothermally repaired to further decompose the alkali-generating compound to form micropores in the skeleton.

Furthermore, if a gelling process is performed by introducing a solvent for micelle formation of an organic polymer together with an organic chain alkoxysilane into an acidic solution, a pseudo fine pore template made of the organic polymer is contained in the skeleton. It can be further enlarged by hydrothermal treatment under alkaline conditions. In addition, it is possible to control the micelle size by changing the type of solvent to be micelle, and thus the pore size in the skeleton can also be controlled.
The resulting double pore porous body can improve the sample load when used in an adsorption medium or the like due to an increase in surface area due to pores in the skeleton.

  In the method for producing a chromatography column according to the present invention, the double pore organic chain inorganic porous material is produced in the capillary using the method for producing a double pore organic chain inorganic porous material of the present invention in the capillary. Since it is formed in a packed state, it is possible to obtain a column with excellent resolution that can be used satisfactorily even in an alkaline region in which the double pore organic chain inorganic porous material of the present invention is densely packed in the capillary. .

  Examples are given below to further clarify the features of the present invention, but the present invention is not limited to these Examples.

(Example 1)
1.1 g of ethylene glycol-propylene glycol block copolymer (BASF brand name Pluronic P123, average molecular weight 5,800) as an organic polymer having phase separation inducing action in 5 ml of 0.01 M acetic acid aqueous solution, and as an alkali-generating compound 0.5 g of urea was dissolved and stirred uniformly to obtain a pH 3.4 acidic solution.
To this acidic solution, 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane was added and stirred to obtain a uniform solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the container was sealed and polycondensed at 60 ° C. for 24 hours to obtain a wet gel having a pH of 7.9.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 10.1 at 150 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried, and calcined at 250 ° C. for 10 hours to obtain a double pore porous body.
When the obtained double pore porous body was observed with an electron microscope, it was found that it had a skeleton in which micron-order continuous pores were formed as shown in FIG.
Moreover, the fine pore diameter in the skeleton of the obtained double pore porous body was measured by a nitrogen adsorption method, and the result is shown in FIG.
From FIG. 2, it is preferable that the obtained double pore porous body is almost occupied by the fine pores formed in the skeleton having a diameter of 10 nm or less, and the majority of those having a diameter of about 8 nm are occupied. all right.

(Example 2)
A solution of 1.8 g of polyoxyethylene nonylphenyl ether as an organic polymer having phase separation-inducing action and 0.5 g of urea as an alkali-generating compound was dissolved in 5.25 ml of 0.01 M acetic acid aqueous solution and stirred uniformly until pH 3 An acidic solution of .4 was obtained.
To this acidic solution, 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane was added and stirred to obtain a uniform solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the container was sealed and polycondensed at 60 ° C. for 24 hours to obtain a wet gel having a pH of 7.7.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 9.7 at 200 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried, and calcined at 250 ° C. for 10 hours to obtain a double pore porous body.
When the obtained double-pore porous body was observed with an electron microscope, it was found that it had a skeleton in which micron-order continuous pores were formed, as shown in FIG.
Moreover, the fine pore diameter in the skeleton of the obtained double pore porous body was measured by a nitrogen adsorption method, and the result is shown in FIG.
As shown in FIG. 4, in the obtained double pore porous body, the fine pores formed in the skeleton are almost occupied by those having a diameter of 10 nm or less, and the majority of those having a diameter of about 3.5 nm are occupied. I understand.

Example 3
2 g of ethylene glycol-propylene glycol block copolymer (BASF brand name Pluronic P123, average molecular weight 5,800) as an organic polymer having phase separation inducing action in 5 ml of 0.01 M acetic acid aqueous solution, and as an alkali-generating compound 1 g of urea was dissolved and stirred uniformly to obtain a pH 3.4 acidic solution.
Add 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane to this acidic solution, stir to make a homogeneous solution, and further a solvent for inducing pore formation by micellizing an organic polymer having a phase separation inducing action As a result, 1.4 ml of trimethylbenzene was added.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the vessel was sealed and polycondensed under 60 ° C. conditions for 24 hours to obtain a wet gel with pH 8.1.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 9.7 at 200 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried, and calcined at 250 ° C. for 10 hours to obtain a double pore porous body.
When the obtained double pore porous body was observed with an electron microscope, it was found that it had a skeleton with micron-order continuous pores as shown in FIG.
Moreover, the fine pore diameter in the skeleton of the obtained double pore porous body was measured by a nitrogen adsorption method, and the result is shown in FIG.
From FIG. 6, it can be seen that in the obtained double pore porous body, the fine pores formed in the skeleton are almost occupied by those having a diameter of 100 nm or less, and the majority of those having a diameter of about 50 nm are occupied. all right. That is, it was found that the pores were enlarged by the addition of trimethylbenzene.

Example 4
Ethylene glycol-propylene glycol block copolymer (BASF brand name Pluronic P123, average molecular weight 5,800) as an organic polymer having an action of inducing phase separation in 4.5 ml of 0.01 M acetic acid aqueous solution, and 2.2 g as an alkali-generating compound 2 g of urea was dissolved and stirred uniformly to obtain a pH 3.4 acidic solution.
Add 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane to this acidic solution, stir to make a homogeneous solution, and further a solvent for inducing pore formation by micellizing an organic polymer having a phase separation inducing action As a result, 1.4 ml of trimethylbenzene was added.
The container containing this homogeneous solution is degassed by irradiating with ultrasonic waves for 5 minutes, and after helium gas replacement is performed for 10 minutes, it is filled into fused silica capillaries with inner diameters of 50 mm ID and 100 mm ID, respectively. Then, both ends of each capillary were sealed and polycondensed under 70 ° C. for 24 hours to obtain a wet gel having a pH of 8.4.
Furthermore, in order to form pores in the skeleton, the capillaries were sealed and subjected to hydrothermal treatment under alkaline conditions at 200 ° C. for 24 hours. The obtained gel of each capillary was washed with a mixed solution of water and methanol, dried, and calcined at 250 ° C. for 10 hours to obtain a chromatography column in which the capillary was filled with the double pore porous material.
When the cross sections of the obtained chromatography columns were observed with an electron microscope, it was found to have a skeleton with micron-order continuous pores as shown in FIGS.
Using each of the obtained capillary columns, normal phase chromatography was performed under a mobile phase condition of 150 mm in column length, hexane / 2-propanol = 98/2, under a linear velocity of 1.1 mm / s and a column pressure of 72 bar. When toluene, 2,6-dinitrotoluene, and 1,2-dinitrobenzene samples were separated, the results shown in FIGS. 9 and 10 were obtained, and it was found that the theoretical plate height was 7.1 mm. That is, this shows that downsizing with a capillary and high performance column can be achieved.

(Example 5)
2.12 g of an ethylene glycol-propylene glycol block copolymer (BASF's product name Pluronic F68, average molecular weight 8,400) as an organic polymer having a phase separation-inducing action in 6 ml of 0.01 M acetic acid aqueous solution, and as an alkali-generating compound 0.725 g of urea was dissolved and stirred uniformly to obtain an acidic solution having a pH of 3.4.
To this acidic solution, 5 ml of methyltrimethoxysilane and 0.25 ml of dimethyldimethoxysilane as organic chain alkoxysilane were added and stirred to obtain a uniform solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the vessel was sealed and polycondensed at 60 ° C. for 24 hours to obtain a wet gel having a pH of 7.8.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 9.7 at 200 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried, and calcined at 250 ° C. for 10 hours to obtain a double pore porous body.
When the obtained double-pore porous body was observed with an electron microscope, it was found that it had a skeleton in which micron-order continuous pores were formed, as shown in FIG.

Example 6
1.1 g of an ethylene glycol-propylene glycol block copolymer (BASF product name Pluronic P123, average molecular weight 5,800) as an organic polymer having a phase separation inducing action in 5.8 ml of 0.1 M nitric acid aqueous solution, and as an alkali-generating compound 0.5 g of urea was dissolved and stirred uniformly to obtain a pH 1.1 acidic solution.
To this acidic solution, 2 ml of 1,2-biz (trimethoxysilyl) ethane as an organic chain alkoxysilane was added and stirred to obtain a homogeneous solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the container was sealed and polycondensed at 60 ° C. for 24 hours to obtain a wet gel having a pH of 1.8.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 10.4 at 110 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried, and calcined at 250 ° C. for 10 hours to obtain a double pore porous body.
When the obtained double pore porous body was observed with an electron microscope, it was found that it had a skeleton in which micron-order continuous pores were formed as shown in FIG.
Moreover, the fine pore diameter in the skeleton of the obtained double pore porous body was measured by a nitrogen adsorption method, and the result is shown in FIG.
From FIG. 13, in the obtained double pore porous body, it is preferable that the fine pores formed in the skeleton are almost occupied by those having a diameter of 10 nm or less, and the majority of those having a diameter of about 7 nm are occupied. all right.

(Example 7)
A solution of 1.8 g of polyoxyethylene nonylphenyl ether as an organic polymer having phase separation-inducing action and 0.5 g of urea as an alkali-generating compound was dissolved in 5.25 ml of 0.01 M acetic acid aqueous solution and stirred uniformly until pH 3 An acidic solution of .4 was obtained.
To this acidic solution, 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane was added and stirred to obtain a uniform solution.
The container in which this homogeneous solution is placed is degassed by irradiating with ultrasonic waves for 5 minutes, and after helium gas replacement is performed for 10 minutes, each is filled into a fused silica capillary with an inner diameter of 50 mm ID, and both ends of the capillary are Was sealed and polycondensed at 60 ° C. for 24 hours to obtain a wet gel having a pH of 7.7.
Furthermore, in order to form pores in the skeleton, each capillary was hydrothermally treated at 200 ° C. for 24 hours under alkaline conditions of pH 9.7. The obtained gel of each capillary was washed with a mixed solution of water and methanol, dried, and calcined at 250 ° C. for 10 hours to obtain a chromatography column in which the capillary was filled with the double pore porous material.

(Comparative Example 1)
Without using urea, 4.5 ml of 1M aqueous nitric acid solution and 3.05 g of polyoxyethylene nonylphenyl ether as an organic polymer having a phase separation-inducing action were stirred and mixed to be homogeneous, and an acidic solution (pH 0.4) A chromatography column was obtained in the same manner as in Example 7 except that it was obtained.
Using the chromatography column obtained in Example 7 and Comparative Example 1 above, reverse phase chromatography was carried out under a mobile phase condition of methanol / water = 80/20, respectively, and uracil and 7 types of alkylbenzene (benzene, toluene, ethylbenzene, When propylbenzene, butylbenzene, amylbenzene, hexylbenzene) samples were separated, when the chromatography column of Comparative Example 1 was used, uracil and each alkylbenzene were separated as shown in FIG. When the chromatography column of Example 7 was used, it was not separated as shown in FIG.
In the case of the chromatography column of Comparative Example 1, this is separated by hydrophobic interaction due to the organic chain facing outward, and in the case of the chromatography column of Example 7, the organic chain faces inward. This suggests that they will not be separated.
Further, using the chromatography column obtained in Example 7 and Comparative Example 1 above, normal phase chromatography was carried out under the mobile phase conditions of hexane / 2-propanol = 98/2, respectively, toluene, 2,6-dinitrotoluene. When the 1,2-dinitrobenzene sample was separated, the chromatographic column of Example 7 shown in FIG. 16 had a higher sample retention capacity than the chromatographic column of Comparative Example 1 shown in FIG. I found it big.
This suggests that the porous porous body of Example 7 has more hydrophilic groups (silanol) than the conventional porous body.

(Comparative Example 2)
0.6 g of polyethylene oxide and 0.5 g of urea were dissolved in 5.5 ml of 0.01 M acetic acid aqueous solution and stirred uniformly to obtain an acidic solution having a pH of 3.4.
To this acidic solution, 5 ml of methyltrimethoxysilane as an organic chain alkoxysilane was added and stirred to obtain a uniform solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the container was sealed and kept at 40 ° C. for 24 hours, but did not gel.

(Comparative Example 3)
0.4 g of polyoxyethylene nonylphenyl ether, 1.1 g of methanol, and 0.5 g of urea were dissolved in 3.3 ml of 1M nitric acid aqueous solution and stirred uniformly to obtain an acidic solution having a pH of 0.4.
To this acidic solution, 10 ml of methyltrimethoxysilane as an organic chain alkoxysilane was added and stirred to obtain a uniform solution.
The container containing the homogeneous solution was deaerated by irradiating with ultrasonic waves for 5 minutes, and helium gas replacement was performed for 10 minutes. Thereafter, the container was sealed and polycondensed at 40 ° C. for 24 hours to obtain a wet gel having a pH of 0.4.
Further, the obtained wet gel was replaced with an aqueous urea solution, and hydrothermal treatment was performed under alkaline conditions of pH 9.7 at 200 ° C. for 24 hours in order to form pores in the skeleton.
The obtained gel was washed with a mixed solution of water and methanol water, dried and fired at 250 ° C. for 10 hours to obtain a porous body.
When the obtained porous body was observed with an electron microscope, it was found that the porous body had a skeleton having micron-order continuous pores as shown in FIG.
Moreover, the fine pore diameter in the skeleton of the obtained porous body was measured by a nitrogen adsorption method, and the result is shown in FIG.
FIG. 19 clearly shows that the obtained porous body has no nm-order pores formed in the skeleton.

  Chromatographic separation medium, porous material for blood separation, sample concentration medium for environmental analysis, porous material for hygroscopic agent, porous material for low molecular weight adsorption such as deodorant, porous material used for membrane emulsification method to produce fine particles with uniform diameter It is suitable for use in porous membranes for enzyme membranes and catalyst carriers.

2 is a scanning electron micrograph of the double pore porous material obtained in Example 1. FIG. It is a figure which shows the pore diameter distribution which measured the micropore in the frame | skeleton of the double pore porous body obtained in Example 1 by the nitrogen adsorption method. 4 is a scanning electron micrograph of the double pore porous material obtained in Example 2. It is a figure which shows the pore diameter distribution which measured the micropore in the frame | skeleton of the double pore porous body obtained in Example 2 by the nitrogen adsorption method. 4 is a scanning electron micrograph of the double pore porous material obtained in Example 3. It is a figure which shows the pore diameter distribution which measured the micropore in the frame | skeleton of the double pore porous body obtained in Example 3 by the nitrogen adsorption method. 4 is a scanning electron micrograph of a cross section of a chromatography column obtained using a fused silica capillary having an inner diameter of 50 mm ID in Example 4. FIG. 4 is a scanning electron micrograph of a cross section of a chromatography column obtained using a fused silica capillary having an inner diameter of 100 mm ID in Example 4. Normal phase chromatography was performed using the chromatographic column obtained using the fused silica capillary with an inner diameter of 50 mm ID in Example 4 to separate samples of toluene, 2,6-dinitrotoluene and 1,2-dinitrobenzene. It is a figure which shows a result. Normal phase chromatography was performed using the chromatographic column obtained using the fused silica capillary of Example 4 with an inner diameter of 100 mm ID to separate toluene, 2,6-dinitrotoluene, and 1,2-dinitrobenzene samples. It is a figure which shows a result. 6 is a scanning electron micrograph of the double pore porous material obtained in Example 5. 6 is a scanning electron micrograph of the double pore porous material obtained in Example 6. It is a figure which shows the pore diameter distribution which measured the micropore in the frame | skeleton of the double pore porous body obtained in Example 6 by the nitrogen adsorption method. It is a figure showing the result of having performed reverse phase chromatography with the column for chromatography obtained in Example 7, and isolate | separating 6 types of alkylbenzene. It is a figure showing the result of having performed reverse phase chromatography with the column for chromatography obtained in comparative example 1, and having separated six kinds of alkylbenzene. It is a figure showing the result of having isolate | separated toluene, 2, 6- dinitrotoluene, and 1, 2- dinitrobenzene by performing normal phase chromatography with the column for chromatography obtained in Example 7. FIG. FIG. 4 is a diagram showing the results of separation of toluene, 2,6-dinitrotoluene, and 1,2-dinitrobenzene by performing normal phase chromatography using the chromatography column obtained in Comparative Example 1. 4 is a scanning electron micrograph of the porous material obtained in Comparative Example 3. It is a figure which shows the pore diameter distribution which measured the micropore in the frame | skeleton of the porous body obtained by the comparative example 3 by the nitrogen adsorption method.

Claims (9)

  A double-pore organic chain inorganic porous material having a three-dimensional network structure skeleton composed of a silane polycondensate having a SiC bond portion in the molecule, and having fine pores in the skeleton. The organic chain alkoxysilane was hydrolyzed by introducing the organic chain alkoxysilane into an acidic solution containing an alkali generating compound that decomposes by heating to generate an alkali component and an organic polymer having a phase separation inducing action. Then, a gelation step of forming a gel having a three-dimensional network structure skeleton by polycondensation of organic chain alkoxysilane while heating to decompose the alkali-generating compound,
A micropore forming step of forming a micropore in the skeleton by hydrothermally treating the obtained gel under alkaline conditions, and a method for producing a double pore organic chain inorganic porous body .   The method for producing a double pore organic chain inorganic porous material according to claim 2, wherein the acidic solution has a pH of 1 or more and less than 5 and the pH during polycondensation is not less than the acidic solution pH before polymerization.   The double pore organic chain inorganic porosity according to claim 2 or 3, wherein the gelling step is performed by introducing a solvent for micelleizing an organic polymer having a phase separation inducing action together with an organic chain alkoxysilane into an acidic solution. A method for producing a mass.   The method for producing a double pore organic chain inorganic porous material according to any one of claims 2 to 4, wherein the alkali-generating compound is urea.   The organic chain alkoxysilane is at least one selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and 1,2-bistrimethoxysilylethane. 6. A process for producing a double pore organic chain inorganic porous material according to any one of 5 above.   The organic polymer is at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyoxyethylene nonyl phenyl ether, and ethylene oxide-propylene oxide copolymer. A method for producing a double pore organic chain inorganic porous material.   The method for producing a double pore organic chain inorganic porous material according to any one of claims 4 to 7, wherein a solvent for micelleizing the organic polymer is at least one of trimethylbenzene and butanol.   The double pore organic chain inorganic porous material is filled in the capillary using the method for producing a double pore organic chain inorganic porous material according to any one of claims 2 to 8 in the capillary. A method for producing a chromatography column, characterized in that the column is formed into a state.